Solid addition compounds for producing smoke and process for forming said compounds



SOLID ADDITION COMPOUNDS FOR PRODUCING SMOKE AND PROCESS FOR FORMING SAID COMPOUNDS Alfred F. Tatyrek, Maplewood, N.J., assignor to the United States of America as represented by the Secretary of the Army No Drawing. Filed June 3, 1966, Ser. No. 555,932

7 Claims. (Cl. 252-305) ABSTRACT OF THE DISCLOSURE Processes for converting smoke-producing liquids such as titanium tetrachloride or vanadium oxytrichloride into solids by causing about 35 to 65 volume percent of the liquid smoke-producing compound to react with about 65 to 35 volume percent of fuming sulfuric acid having a concentration of about 40 to 80 percent, the reaction being brought about by stirring the chloride with the acid for a few seconds.

This invention relates to pyrotechnics and more particularly concerns methods of converting smoke producing liquids into more useable and highly desirable solid compounds.

Titanium tetrachloride and vanadium oxytrichloride are well known highly reactive hydrolyzable metal chloride compounds finding utility as liquid smoke producing agents. Titanium tetrachloride (TiCh) has been used to produce white smoke clouds. It evaporates and undergoes hydrolysis with the moisture of the air, for example, to produce voluminous and dense white smoke consisting of hydrated titanium dioxide and hydrogen chloride fumes. Since this noncombustion type reaction proceeds rapidly under very nearly all conditions of temperature and humidity found on the earths surface to liberate extensive quantities of smoke, and requires no initiation, it would be most advantageous if liquid TiCl could be readily converted to the more useable and desirable solid form.

Similarly, liquid vanadium oxytrichloride (VOCl produces an intense orange color smoke. The liquid forms, however, of both aforementioned smoke producing compounds suffer many disadvantages, due to high vapor pressures thereof providing:

(a) Undesirably rapid rate of vaporization (b) Excessive leakage in their packaging (c) Handling difiiculties (d) Aerodynamic heating during rocket or projectile containing these variations in liquid vapor pressure.

Further, the aforementioned disadvantages are not completely overcome when thickening agents such as silica gel or adsorbers, such as nylon or glass fibers are added to the liquid compounds. In addition, the solid component of these physical mixtures is inert insofar as production of smoke is concerned.

It is therefore a broad object of the invention to provide smoke producing compounds suffering none of, or a least substantially eliminating, the disadvantages aforementioned.

Another object of the invention is to provide methods of converting various liquid smoke producing compounds into solid compounds.

Still another object of the invention is to provide methods for converting various liquid smoke producing compounds into solids employing readily available chemicals, said methods being inexpensive, rapid and eflicient.

Other objects and advantages of the invention will be apparent as the description of the invention proceeds.

In accordance with the above objects, I have discovered that certain highly reactive liquid hydrolyzable metal chloballistic flight of a liquids and causing nited States Patent O 3,402,129 Patented Sept. 17, 1968 ride compounds, when reacted with fuming sulfuric acid will produce a hard and gummy sulfur trioxide addition compound possessing all the smoke producing qualities of the original liquid metal chloride compound.

More specifically, when TiCl and V001 are caused to react with fuming sulfuric acid, solid TiCl -SO and VOCl -nSO are readily and economically produced.

Although it is not intended that the invention be limited thereto, there is set forth hereinbelow, for purpose of illustration, examples of procedures which may be used in practicing my invention.

Example I At room temperature under a hood, 10 cc. of TiCl was placed into a 300 cc. glass beaker and 10 cc. of 65% fuming sulfuric acid (H SO -SO slowly poured therein, the contents being carefully stirred as long as possible before a product is formed. Within, however, a period of about four seconds, a slurry formed and in less than nine seconds, a final product weighing about 36 /2 grams and having a structure resembling frozen butter formed.

The reaction may be characterized as follows:

TiCh Tron-s03 HzSO4-SOa TiCl -SO is a solid compound and will contain H 50 therewithin. The preferred fuming sulfuric acid (H SO -SO concentration is about 65%, i.e., 35% actual H and 65% free S0 The effective concen tration of fuming sulfuric acid may vary between about 40 to 80%, although about 60 to 70% has been found more effective. Concentrations below about 40% will not form solid addition compounds of etiher TiCl or VOCl The reaction above is probably one of addition of the S0 to TiCL; with the sulfuric acid acting as a carrier for S0 Liquid carriers for the 80;, other than sulfuric acid have been successfully used. However, the processes described in this invention have been found most desirable. Of course, when the fuming sulfuric acid concentration is raised to about 70%, the free S0 is increased and accordingly lesser quantities of the acid will be necessary to produce the desired reaction. The reaction will also be slightly accelerated.

When the final solid product reacts with moisture, large quantities of white smoke are evolved in accordance with the following equation:

Example II At room temperature under a hood, 12 cc. of VOCl was placed into a 300 cc. glass beaker and 8 cc. of 70% fuming sulfuric acid carefully poured therein while the contents were constantly stirred. In about 3 /2 seconds, a thick slurry was formed and an additional 2 /2 seconds produced a hard and gummy solid. The reaction may be characterized:

VOCla V0 Ola-M3 3) The value of (n) is not known. The final addition product, however, is a solid. When the solid reacts with water an orange smoke is produced:

' S03 V205 (hydrated) 2H2SO4 When the fuming sulfuric acid concentration resides between about 40 to 80%, the effective range of TiCl and VOCl will vary between about 35 to 55 volume percent when 65% fuming sulfuric acid is used; approximately equal volumes of either TiCl or VOCl will yield the respective solid addition product having optimium smoke producing and handling properties.

The final product may readily be pressed into desired hardware items under conditions of very low humidity. If necessary, my solid products may even be machined, and if the H 50 contained therewithin is removed, may even be pulverized into granular pellets or powder.

I claim:

1. A process for forming a sulfur trioxide addition compound of a highly reactive liquid hydrolyzable metal chloride selected from the group consisting of TiCl and VOCL'; comprising reacting about to 65 volume percent of said chloride with about 65 to 35 volume percent of fuming sulfuric acid having a concentration ranging between about 40 to 80%.

2. The process as described in claim 1 wherein said chloride consists of TiCl said volume percents are percent each for said chloride and said acid concentration is about 3. The process as described in claim 2 wherein said TiCL; and acid is stirred for about three seconds to form a slurry, and

stirred for about an additional four seconds to produce a solid compound.

4. The process as described in claim 1 wherein said chloride consists of VOCl said volume percents are 60 percent and 40 percent by liquid VOCl for said chloride and said acid, respectively, and said acid has a concentration of about 5. The process as described in claim 4 wherein said VOC1 and acid are stirred for about 3 /2 seconds to form a thick slurry, and stirred for about an additional 2 /2 seconds to produce a solid compound.

6. The solid smoke-producing compound TiCLySO 7. The solid smoke-producing compound VOCl -n(SO where n is at least 1.

References Cited UNITED STATES PATENTS 2,175,790 10/1939 Booker et al 252305 LEON D. ROSDOL, Primary Examiner.

R. D. LOVERING, Assistant Examiner. 

